JPS5845275A - Acrylic adhesive - Google Patents

Abstract

PURPOSE:The titled adhesive, consisting of a homologous polymer consisting of a compound expressed by a specific formula or a copolymer consisting of the compound and another compound expressed by a specific formula, and having a specified intrinsic viscosity and improved water and oil resistance. CONSTITUTION:An adhesive consisting of (A) a homologous polymer consisting of a compound expressed by formulaI{R<1> is H, methyl, ethyl, or propyl; (l) is an integer 1-5; (s) is 0 or 1; Rf is -(CF2)mX or -(CF2)pO(CF2)nF[(m) is an integer 1-10; X is H, F or hexafluoropropyl; (n) is an integer 1-5; (p) is an integer 1-3]}, e.g. pentafluoropropyl acrylate, or a copolymer consisting of the component (A) and (B) a compound expressed by formula II (R<2> is H, methyl, ethyl or propyl; R<3> is ON, NH2, NHCH2OH, formula III, etc.), e.g. acrylamide, and having an intrinsic viscosity of 0.1-1.0. The content of the component (A) in the polymer is preferably 30-100mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an acrylic adhesive used in pressure-sensitive adhesive tapes and the like.

Adhesives based on rubbers such as natural rubber, butylene rubber, acrylonitrile rubber, chloroprene rubber, nutylene-butadiene copolymer rubber, urethane rubber, or polyvinyl ether, polyvinyl butyral, polyvinyl chloride, vinyl chloride-vinyl acetate. Adhesives made by adding rosin, rosin ester, natural resins, oil-soluble phenol resins, etc. as tackifiers to copolymers, and acrylic adhesives such as polyacrylic esters are known.

However, these adhesives have the disadvantage of insufficient oil resistance and moisture resistance, and are not suitable for use in environments where oil mist is generated or high humidity. Currently, it is hardly used in these fields.

An object of the present invention is to provide an acrylic pressure-sensitive adhesive that eliminates these drawbacks.

(a) at least one formula: [wherein R1 is hydrogen, methyl, ethyl or butyl;
is an integer from 1 to 5, S is 0 or 1, Rf is (CF 2
) p O (CF2 ) n F (here, m is 1 to 1
o is an integer; X is hydrogen, fluorine or hexafluoroisofurohyl; Y is fluorine or trifluoromethyl; n is an integer of 1 to 5; ] A homologous polymer consisting of a compound represented by, or (a) and (b) at least one formula: [wherein R2 is hydrogen, methyl, ethyl, or CH2CH20H, CH2CH
CHB i represents CH2CH2N(CH3)2. ] This is achieved by using an acrylic pressure-sensitive adhesive made of a copolymer made of a compound represented by the following formula and having an intrinsic viscosity of 0.1 to 1.0.

Therefore, the acrylic pressure-sensitive adhesive of the present invention has water resistance or moisture resistance, and also contains nonpolar hydrocarbons such as petroleum benzine, gasoline, benzene, toluene, and xylene, and alcohols such as methanol, ethanol, and butanol. , and other edible oils and mineral ξ. Specific examples of monomer (I) of the polymer used in the present invention include 2.2.8.8.4.4.5 .5-octafluoropentyl acrylate, 2.2.8.8.8-pentafluoropropyl acrylate, 2.2.3.3.4.
4.4-Heptafluorobutyl acrylate, 2.2.
8.4.4゜4-hexafluorobutyl acrylate,
2,2,8°8,4.5.5.5-octafluoro-4
-trifluoromethylpentyl acrylate, 1. l-
Sibaido 2,4-trifluoromethyl-3,6-oxaperfluorononyl acrylate, 1,1-Sibaido 2.4.7-)lifluoromethyl-8,6,
9-Oxaperfluorododecyl acrylate, 1.1
-Sibidero 2.4,7.10-) Lifluoromethyl-3,6゜9.12-oxaperfluoropentadecyl acrylate, 5.5.6.6.7.7.7-hebutafluoro-3-oxaheptyl acrylate , 2.2.
3. :13.5.5.5-heptafluoro-4-oxapentyl acrylate), 1.1-dihydrononafluoro 4-oxahexyl acrylate, 1.1-dihydroundecafluoro 4-oxaheptyl Examples include acrylate and the above-mentioned methacrylates, 2-ethyl acrylate, 2-propyl acrylate, and other fluoroacrylates, fluoromethacrylate, fluoro-2-ethyl acrylate, fluoro-2-propyl acrylate, and the like.

Monomer (1) is used alone or in combination of two or more, and the fluorine content in the homologous polymer or copolymer with monomer (Il) is at least 20% by weight, preferably at least 45
Exhibits excellent oil resistance at a composition of % by weight. If the fluorine content is lower than this, the oil resistance will decrease, which is undesirable. Furthermore, if the prime number of Rf exceeds 1O, the polymerization rate decreases and the oil resistance does not improve significantly, which is disadvantageous.

When making a copolymer with monomer […], monomer [1]
The content may be determined arbitrarily depending on the oil resistance and moisture resistance required of the adhesive, but if it is too small, the oil resistance and moisture resistance will be too low, so it is usually at least 30.
mol %, preferably at least 70 mol %.

Specific examples of monomer (II) include acrylic acid, acrylamide, N-methylol acrylamide, methacrylic acid, methacrylamide-2-ethyl acrylic acid, 2-ethylacrylamide, 2-propylacrylic acid, and 2-propylacrylamide. monomer LID”]
is used to strengthen the adhesion and adhesion of the adhesive to the support and to adjust the cohesive force of the polymer.

If the intrinsic viscosity [η] of the polymer is too large, the polymer becomes elastic and loses its adhesive properties, making it unsuitable for use as an adhesive. Furthermore, if the intrinsic viscosity is too low, the cohesive force of the polymer will be low, and in this case as well, it is unsuitable for use as an adhesive. Therefore, a polymer having an intrinsic viscosity of 0.1 to 1.0 is preferable as an adhesive.

The glass transition point of the polymer used in the present invention is appropriately determined according to the temperature range in which the adhesive is used. That is, the glass transition point of the polymer is required to be lower than any of the operating temperatures. With the pressure-sensitive adhesive of the present invention, the temperature can be adjusted within the range of -60°C to +90°C. In the normal operating temperature range of pressure-sensitive adhesives, it is sufficient that the glass transition point is -5°C or lower.

The pressure-sensitive adhesive of the present invention can be produced by a conventional polymerization method such as emulsion polymerization, solution polymerization or bulk polymerization of monomer (1') alone or monomer [1.] and monomer [11]. It is carried out by polymerization. For emulsion polymerization, anionic emulsifiers such as alkyl sulfate ester soda, polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, etc. are added as an emulsifier to water deoxygenated by nitrogen substitution as necessary. Nonionic emulsifiers can be used.

In the case of solution polymerization, a halogenated solvent such as 1,1,2-)lifluoro-1,2,2-trichloroethane or hexafluorometa-xylene, or methyl ethyl ketone, methyl isobutyl ketone, Polymerization can be carried out using polar solvents such as ethyl acetate, butyl acetate, and tetrahydrofuran alone or in combination.

Polymerization catalysts include hydrogen peroxide, benzoyl peroxide,
Peroxides such as di[-butyl peroxide', cumene hydroxyperoxide, perIXt(m salts) such as ammonium persulfate, potassium persulfate, and azobisisobutyronitrile, 4,4-azobis(4-cyanovalerian) Azo compounds such as acid) are used, and 0 per total monomer.
．． It is added at a rate of 01-5%.

The intrinsic viscosity 5 can be adjusted by adjusting the polymerization catalyst concentration 2, adjusting the polymerization temperature, or using a chain transfer agent. In the case of solution polymerization, in addition to the above, it can also be carried out by adjusting the ratio of monomer and solvent. As the chain transfer agent, long chain mercaptans such as lauryl mercaptan and myristyl norcaptan tyl mercaptan are preferably used, and preferably 0.01% per total monomer.
It is added in a proportion of ~5% by weight.

In order to adjust the glass transition point (Tg), copolymerization may be performed to obtain a composition calculated from the Tg of each homopolymer using the following formula.

[Here, Wl is the weight fraction of homopolymer 1, W2 is the weight fraction of homopolymer 2, and Tgl is the Tg ('
K), Tg2 are Tg ('K), Tgl of homopolymer 2
2 is the Tg ('K) of the copolymer. ) The intrinsic viscosity of the obtained polymer was measured at 35°C using methyl ethyl ketone (MEK) or meta-xylene hexafluoride as a solvent. The unit is (d//g).As a solvent, it is appropriate to use a solvent that gives a large value of intrinsic viscosity as a result of measurement.A solvent that gives a large value of intrinsic viscosity is a good solvent; This is because the measurement is carried out in a good solvent.In the polymer according to the present invention, it is generally better to use metaxylene hexafluoride when the number of carbon atoms in Rf is 8 or more, and to use methyl ethyl ketone when the number of carbon atoms in Rf is 7 or less. , this is not necessarily the case.

The adhesive according to the present invention can adhere to various base materials. For example, polytetrafluoroethylene, hexafluoropropene-tetrafluoroethylene copolymer,
Fluorocarbon polymers such as polyvinyl fluoride, polyvinylidene fluoride, and fluororubber, general-purpose resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyester, amide resin, urea resin, phenol resin, and melamine resin, cellophane, Semi-synthetic fibers such as rayon, natural fibers such as cotton, silk, and wool, other woven fabrics,
These include paper, metal, glass, china, ceramics, timber, and leather.

Therefore, in order to apply the adhesive of the present invention to the above base material,
That'=! Alternatively, it can be diluted with a solvent and then applied. As the solvent, a solvent used in solution polymerization can be used.

Next, examples and comparative examples will be shown to specifically explain the present invention.

Example 1 A 30-liter vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser
In a 0ml four-eye flask, add 100 g of butyl acetate, 80 g of pentafluoropropyl acrylate monomer, and n-
Charge 0.1 g of dodecyl mercaptan, replace the air in the system with nitrogen, and raise the temperature to 60°C. When the specified temperature was reached, 0.15 g of azobisisobutyronitrile (AIBN) and 10 rn of butyl acetate were added from the dropping funnel. Add solution. After continuing the polymerization for about 10 hours, the contents were taken out and poured into petroleum ether to precipitate the polymer. After drying, 23 g of pentafluoropropyl acrylate polymer (
1g5-26°C1[η]0.6/in MEK) was obtained.

Next, 20 g of the obtained polymer was dissolved in 80 g of trifluorotrichloroethane/butyl acetate (2/1 (weight ratio)), and the solution was applied to a corona discharge-treated polyester film having a thickness of 150 μm and dried. The thickness of the acrylate polymer was approximately 25μ.

Neoflon film (tetrafluoroethylene-hexafluoropropylene copolymer: Daikin Industries, Ltd.)
was crimped from the top with a pressure of 2 kQ/c4, cut into 50 strips, and the adhesive strength was measured. The measurement conditions used here were 180° peeling and tensile rate; aOO mm/min.

For the oil resistance test and the water resistance test, a 50-shoulder cut test piece was immersed in a predetermined solvent for 2 hours, then taken out, and the adhesive force was measured under the above measurement conditions to calculate the adhesive force retention rate. The results are shown in Table 3.

Examples 2 to 20 It has the monomer composition shown in the first person and Table 2, and has the Tgl intrinsic viscosity shown in the same table (measured in MEK, but in Example 11, in metaxylene hexafluorite) and fluorine. Adhesive force measurement and oil resistance and water resistance tests were conducted in the same manner as in Example 1 using the same amount of polymer. The results are shown in Table 3.

Comparative Examples 1 to 7 In Comparative Examples 1 to 5, polymers having the monomer compositions shown in Table 4 were used, and in Comparative Examples 6 and 7, adhesive strength was measured and measured in the same manner as in Example 1 using the tapes shown in the same table. Oil and water resistance tests were conducted. The results are shown in Table 5.

Procedural amendment (Jigen, Director General of the Japan Patent Office 1) Indication of the case 1982 Patent Application No. 143342 2 Name of the invention Acrylic adhesive 3, Person making the amendment Relationship to the case Patent applicant's principal office Irisaka City, Osaka Prefecture 1e ward tin !II 1-chome [me 2
This No. 39 New page 1 Rapid Building Name (285) Daikin Industries “1ζ Ceremony Committee Representative Yama 1) t≧4 Agent 5, Date of Amendment Order (Voluntary) 7 The following passages in the internal medicine clear axis of amendment Correct it.

■Claims column As per attached sheet.

■ In the Detailed Description of the Invention column, lines 5-4 at the end of page 3 and lines 1-2 at the bottom of 4-ryo formula (n), the word "butyl" has been corrected to "propyl."

Above (attached sheet) Claim 1, (al at least one type [wherein kl is hydrogen, methyl, ethyl or propyl,
t is an integer from 1 to 5, S is O or 1, Rf is -(CF2
)PO(CF2)nF (where m is an integer of 1 to 10, X is hydrogen, fluorine or hexafluoroisopropyl, Y is fluorine or trifluoromethyl, n is 1 to 5
P is an integer from 1 to 3). ] A homologous polymer consisting of a compound represented by (a) and (bl) at least one type [wherein k2 is hydrogen, methyl, ethyl or H CH2CH20H, CH2CHCH3 or CHCHN
(CH3)2 represents. [2] An acrylic pressure-sensitive adhesive comprising a copolymer comprising a compound represented by 2 and having an intrinsic viscosity of 0.1 to 1.0.

2. The adhesive according to claim 1, wherein the content of +3+ in the polymer is 30 to 100 mol%.

− Procedural amendment @ (voluntary) January 1982
February ・1 [1 Mr. Commissioner of the Japan Patent Office 1, Indication of the case, Patent Application No. 143342 of 1982, 2, Name of the invention, acrylic adhesive 3, Relationship with the person making the amendment Patent applicant address: Osaka City, Osaka Prefecture Kita-ku Umeda 1-12:39 New Hankyu Building Name (285> Daikin Industries, Ltd. Representative 1
11 1) Minoru □2, 1'' 5. Date of amendment order: (Voluntary) 6. Subject of amendment 1. The following parts of the detailed statement of amendment will be amended.

(2) Claims column As per appendix II, Detailed description of the invention column (2), page 4, lines 1-2, "Y is...methyl" was deleted.

” and corrected.

Above (Attachment) Claim 1(a) At least one type [wherein 1 is hydrogen, methyl, ethyl or propyl, l
is an integer from 1 to 5, S is 0 or 1, k [is -(CF2)
or -(CF2), 0(CF2].F (where m is an integer of 1 to 10, X is hydrogen, fluorine or hexafluoroisopropyl, n is an integer of 1 to 5, P is 1 to 3 ), or (a) and (b) at least one of 2 [wherein R2 is hydrogen, methinopeethyl or pro0C]
(2G) (20H, (Horse CHC win or 96I (2
Represents CH2N(CH3)2. ] A copolymer comprising the compound shown in Attachment (1) and having an intrinsic viscosity of 0.1 to 1.0.

The pressure-sensitive adhesive according to claim 1, wherein the content of (a) in the dipolymer is 30 to 10 mol.

Claims (1)

[Claims] 1. (a) At least one type [wherein R1 is hydrogen, methyl, ethyl butyl, l
is an integer from 1 to 5, S is 0 or l, Rf is -(CF2)
PO(CF2)nF (where m is an integer of 1 to 10, X is hydrogen, fluorine or hexafluoroisopropyl, Y is fluorine or trifluoromethyl, n is an integer of 1 to 5, P is an integer of 1 to 3 is an integer). ] A homologous polymer consisting of a compound represented by (a) and (b) at least one [wherein is hydrogen, methyl, ethyl or butyl] CH2CH20H, CH2CHCH3 or CH2CH
Represents 2N(CH3)2. An acrylic/thread adhesive comprising a copolymer comprising a compound represented by the following formula and having an intrinsic viscosity of 0.1 to 1.0. 2. The adhesive according to claim 1, wherein the content of (a) in the polymer is 30 to 100 mol%.